Methods for forming single crystal silicon ingots with improved resistivity control

ABSTRACT

Methods for forming single crystal silicon ingots with improved resistivity control and, in particular, methods that involve gallium or indium doping are disclosed. In some embodiments, the ingots are characterized by a relatively high resistivity.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/439,743, filed Dec. 28, 2016, which is incorporatedherein by reference in its entirety.

FIELD OF THE DISCLOSURE

The field of the disclosure relates to methods for forming singlecrystal silicon ingots with improved resistivity control and, inparticular, methods that involve gallium or indium doping. In someembodiments, the ingots are characterized by a relatively highresistivity.

BACKGROUND

Single crystal silicon, which is the starting material for mostprocesses for the fabrication of semiconductor electronic components, iscommonly prepared by the so-called Czochralski (CZ) process wherein asingle seed crystal is immersed into molten silicon and then grown byslow extraction. Molten silicon is contaminated with various impurities,among which is mainly oxygen, during the time it is contained in aquartz crucible. Some applications, such as advanced wirelesscommunication applications, insulated gate bipolar transistors (IGBT)and low power, low leakage devices, require wafers with a relativelyhigh resistivity such as 1500 ohm-cm (Ω-cm) or more. Productspecifications may require a wafer target resistivity within a toleranceof about 300 Ω-cm or may require a minimum resistivity. Productspecifications also may require that the material does not change type(i.e., P-type to N-type or vice versa) in a given lot of wafers.

As a crystal is grown using the Czochralski method, impurities in themelt may segregate due to a segregation coefficient which causes theimpurity to concentrate in the melt which causes the amount incorporatedinto the ingot to increase as the ingot is grown. This impurity/dopantsegregation effect causes the resistivity of the ingot to change overits length. Further, different impurities in the melt may segregate atdifferent rates which causes their ratio to vary over its length whichmay cause a type change in the ingot. This causes a portion of the ingotto fall outside of product specifications which increases the“non-prime” portion of the ingot.

Highly pure polysilicon is used for high resistivity ingot production.Highly pure polysilicon is characterized by a spread in the impurityprofile which causes a wide spread in the intrinsic resistivity range ofthe un-doped material and its type. Further, for relatively highresistivity wafers such as above 1500 ohm-cm or more, addition ofadditional dopant to control the resistivity and ingot type may bedifficult as very small amounts of dopants are added so as to maintainthe high resistivity of the ingot.

A need exists for methods for preparing high resistivity silicon ingotsthat increase the prime portion of the ingot and that allow for betterresistivity control and/or that simplify extrinsic doping processes.

This section is intended to introduce the reader to various aspects ofart that may be related to various aspects of the disclosure, which aredescribed and/or claimed below. This discussion is believed to behelpful in providing the reader with background information tofacilitate a better understanding of the various aspects of the presentdisclosure. Accordingly, it should be understood that these statementsare to be read in this light, and not as admissions of prior art.

SUMMARY

One aspect of the present disclosure is directed to a method forproducing a single crystal silicon ingot from a silicon melt held withina crucible. Polycrystalline silicon is added to the crucible. Thepolycrystalline silicon is heated to cause a silicon melt to form in thecrucible. A first dopant selected from the group consisting of galliumand indium is added to the crucible. A sample ingot is pulled from themelt. The resistivity of the sample ingot is measured. A second dopantis added to the silicon melt. The amount of second dopant added to themelt is based in part on the measured resistivity of the sample ingot. Aproduct ingot is pulled from the melt.

Another aspect of the present disclosure is directed to a method forproducing a single crystal silicon ingot from a silicon melt held withina crucible. Polycrystalline silicon is added to the crucible. Thepolycrystalline silicon is heated to cause a silicon melt to form in thecrucible. An alloy selected from the group consisting of silicon-galliumand silicon-indium is added to the crucible. A product ingot is pulledfrom the melt.

Various refinements exist of the features noted in relation to theabove-mentioned aspects of the present disclosure. Further features mayalso be incorporated in the above-mentioned aspects of the presentdisclosure as well. These refinements and additional features may existindividually or in any combination. For instance, various featuresdiscussed below in relation to any of the illustrated embodiments of thepresent disclosure may be incorporated into any of the above-describedaspects of the present disclosure, alone or in any combination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic side view of a pulling apparatus for forming asingle crystal silicon ingot;

FIG. 2 is a binary phase diagram for silicon containing impurity “A”that has a segregation coefficient less than 1;

FIG. 3 is the concentration profile of impurity A in the silicon solidfraction;

FIG. 4 is the resistivity profile of the solidified solid fraction;

FIGS. 5-8 are diagrams of the resistivity profiles of ingots with andwithout gallium doping as described in Example 1;

FIG. 9 is a diagram showing the composition segregation curves forboron, phosphorous and gallium for an ingot produced according toExample 1;

FIG. 10 is a diagram of the resistivity profile of ingots with andwithout gallium doping with oxygen donors contributing to theresistivity as described in Example 1;

FIG. 11 is a diagram showing the modeled and measured resistivityprofiles for a gallium compensated system with thermal donor effects;and

FIG. 12 is a photo of granular gallium-silicon alloy prepared accordingto Example 2.

Corresponding reference characters indicate corresponding partsthroughout the drawings.

DETAILED DESCRIPTION

Provisions of the present disclosure relate to methods for producing asingle crystal silicon ingot by the Czochralski method in which galliumor indium are used to compensate for impurities in the polysiliconstarting material. In some aspects, gallium or indium is added as asolid-phase alloy to allow relatively small amounts of the dopant to beadded. In these or in other embodiments, gallium or indium is addedbefore a sample or pilot ingot is produced to determine the resistivityof the melt before addition of other dopants.

In accordance with embodiments of the present disclosure and withreference to FIG. 1, the ingot is grown by the so-called Czochralskiprocess in which the ingot is withdrawn from a silicon melt 44 heldwithin a crucible 22 of a crystal puller 23.

The ingot puller 23 includes a housing 25 that defines a crystal growthchamber 16 and a pull chamber 20 having a smaller transverse dimensionthan the growth chamber. The growth chamber 16 has a generally domeshaped upper wall 45 transitioning from the growth chamber 16 to thenarrowed pull chamber 20. The ingot puller 23 includes an inlet port 7and an outlet port 11 which may be used to introduce and remove aprocess gas to and from the housing 25 during crystal growth.

The crucible 22 within the ingot puller 23 contains the silicon melt 44from which a silicon ingot is drawn. The silicon melt 44 is obtained bymelting polycrystalline silicon charged to the crucible 22. The crucible22 is mounted on a turntable 29 for rotation of the crucible about acentral longitudinal axis X of the ingot puller 23.

A heating system 39 (e.g., an electrical resistance heater 39) surroundsthe crucible 22 for melting the silicon charge to produce the melt 44.The heater 39 may also extend below the crucible as shown in U.S. Pat.No. 8,317,919. The heater 39 is controlled by a control system (notshown) so that the temperature of the melt 44 is precisely controlledthroughout the pulling process. Insulation (not shown) surrounding theheater 39 may reduce the amount of heat lost through the housing 25. Theingot puller 23 may also include a heat shield assembly (not shown)above the melt surface for shielding the ingot from the heat of thecrucible 22 to increase the axial temperature gradient at the solid-meltinterface.

A pulling mechanism (not shown) is attached to a pull wire 24 thatextends down from the mechanism. The mechanism is capable of raising andlowering the pull wire 24. The ingot puller 23 may have a pull shaftrather than a wire, depending upon the type of puller. The pull wire 24terminates in a pulling assembly 58 that includes a seed crystal chuck32 which holds a seed crystal 6 used to grow the silicon ingot. Ingrowing the ingot, the pulling mechanism lowers the seed crystal 6 untilit contacts the surface of the silicon melt 44. Once the seed crystal 6begins to melt, the pulling mechanism slowly raises the seed crystal upthrough the growth chamber 16 and pull chamber 20 to grow themonocrystalline ingot. The speed at which the pulling mechanism rotatesthe seed crystal 6 and the speed at which the pulling mechanism raisesthe seed crystal (i.e., the pull rate v) are controlled by the controlsystem.

A process gas is introduced through the inlet port 7 into the housing 25and is withdrawn from the outlet port 11. The process gas creates anatmosphere within the housing and the melt and atmosphere form amelt-gas interface. The outlet port 11 is in fluid communication with anexhaust system (not shown) of the ingot puller.

In this regard, the crystal puller 23 shown in FIG. 1 and describedherein is exemplary and other crystal puller configurations andarrangements may be used to pull a single crystal silicon ingot from amelt unless stated otherwise.

Impurities in the melt 44, which can act as dopants in the crystal,segregate into the crystal as part of normal freezing or normal crystalgrowth. The segregation of an impurity, impurity “A”, into the crystalis illustrated in FIG. 2. FIG. 2 shows the temperature plotted againstthe composition in a silicon-A system. For this mixture, the boundariesare phase boundaries representing the solidus and liquidus. Attemperatures below the solidus, the mixture is all solid. Conversely, attemperatures above the liquidus, the mixture is all liquid. For a giventemperature, shown as Tx, the segregation coefficient is defined as theratio of the concentration of A in the solid [C_(A)]_(s) to theconcentration of A in the liquid, [C_(A)]_(L).

Thus the segregation is defined by a segregation coefficient, k_(o),where k_(o)=[C_(A)]_(s)/[C_(A)]_(L). Under what is known as “normal”freezing in Czochralski crystal growth, the concentration of impurity Ain the solid can be represented as a function of the fraction solidifiedusing the following:[C]_(s)=k_(o)[C]_(o)(1−g)^(ko-1)  (Eq. 1)wherein [C]_(s) is the concentration of impurity A in the solid, at achosen fraction solidified, g, for a starting concentration of impurityA in the initial liquid, [C]_(o). Knowing the segregation coefficientfor impurity A, and the starting liquid concentration, the concentrationfor increasing fraction solidified can be determined. For an impuritywith a segregation coefficient less than one, a typical behavior of theconcentration profile of A in the solid is shown in FIG. 3.

The resistivity is related to the concentration of the dopant element byresistivity=1/(nqu)  (Eq. 2)where n is the number of charge carriers, q is the fundamental coulombiccharge, and u is the mobility of the charge carrier. Typically thedopant is considered to be fully ionized, and n can be taken as equal tothe concentration of the dopant of interest. A resistivity profile canbe represented as in FIG. 4.

As multiple elements can be present as donors or acceptors, a netmajority of carriers can be calculated as an absolute value asn _(net) =|n _(donors) −n _(acceptors)|  (Eq. 3).If the number of donors exceeds the number of acceptors, then theresistivity may be calculated asResistivity=(n _(net) qu _(e′))  (Eq. 4)where u_(e′) is the mobility of electrons. Conversely, if the number ofdonors is less than the number of acceptors, then the resistivity may becalculated asResistivity=1/(n _(net) qu _(h-si o))  (Eq. 5)where u_(h) _(o) is the mobility of holes.

Given the normal freezing model, it can be seen that for a fixed initialconcentration in a multi-dopant system, the concentration profilesegregated into the solid as a function of fraction solidified will beregulated by the segregation coefficient for the element of interest.Concentration profiles in the solid, even with starting liquidconcentrations being equal, will result in non-equal accumulation of therespective dopants in the solid. Since the resistivity is a netsummation of dopants, and thermal donors from oxygen, the crystal type(i.e. n-type or p-type) can change with increasing fraction solidified,as well as extremely large changes in the resistivity.

Polycrystalline silicon used as feedstock to prepare the melt 44 inCzochralski crystal pulling methods may include intrinsic amounts ofboron, a P-type dopant, and phosphorous, an N-type dopant. Phosphoroushas a segregation coefficient (0.35) that is less than boron (0.80)which causes phosphorous to accumulate relative to boron. As shown inFIG. 5, the first portion of the ingot may be P-type. As phosphorousaccumulates, it compensates for boron causing a spike in resistivity,after which the ingot is N-type.

In order to compensate for large resistivity changes in systemscontaining such as boron and phosphorus, as well as avoiding the crystaltype changing due to the difference in segregation coefficients, inembodiments of the present disclosure, a dopant such as gallium orindium which has a smaller segregation coefficient (0.008, 4×10⁻⁴,respectively) than impurities such as boron and phosphorous is added tothe crucible before the ingot is grown.

For resistivity ranges associated with high resistivity semiconductorproducts, gallium compensation together with phosphorous and boron aswell as sustaining oxygen below 4 nppma or even below 3.5 nppma, lessthan about 3 nppma or less than about 2.5 nppma can result in avoidingtype change within the crystal as well as reduce large changes in theresistivity.

In accordance with embodiments of the present disclosure,polycrystalline silicon is added to the crucible 22. The polycrystallinesilicon is heated to cause silicon to liquefy and form a melt in thecrucible. A first dopant selected from the group consisting of galliumand/or indium is added to the crucible (before or after melting of thepolycrystalline silicon). A sample ingot or “rod” is pulled from themelt and the resistivity of the sample rod is measured. A second dopantis added to the melt, with the amount of second dopant added to the meltbeing based, in part, on the measured resistivity of the sample rod and,in part, the desired resistivity of the product ingot. A product ingotis then pulled from the melt with at least a portion of the body portionof the ingot having a desired, target resistivity.

The polysilicon to which the first dopant is added and from which asample ingot and product ingot is pulled may be semiconductor gradepolysilicon. When semiconductor grade polysilicon is used, in someembodiments the polysilicon has a resistivity greater than 4,000 Ω-cmand contains no more than 0.02 ppba boron or phosphorous. The total bulkmetal content in such polysilicon may be preferably less than 2 ppma.

In some embodiments, the first dopant that is added to the crucible isgallium. Generally, a relatively small amount of gallium is added to thecrucible. For example, the melt may contain less than about 0.5 ppmagallium (as measured after addition of gallium and before pulling of thesample ingot) or even less than about 0.1 ppma, less than 0.01 ppma orless than about 0.001 ppma gallium. In some embodiments, theconcentration of gallium in the melt after gallium addition is fromabout 0.00001 ppma to about 0.5 ppma or from about 0.0001 ppma to about0.1 ppma. In this regard, the stated concentration ranges of gallium(and indium below) are exemplary and the amount of gallium may be chosenbased, in part, on the desired resistivity and the amount of otherelectroactive dopants (e.g., boron, phosphorous, aluminum and the like).

In terms of volume concentration, the resulting melt may have a galliumconcentration of less than about 5×10¹⁵ atoms/cm³, less than about1×10¹⁵ atoms/cm³, less than about 5×10¹⁴ atoms/cm³ or less than about1×10¹⁴ atoms/cm³.

Alternatively or in addition to gallium, indium may be used as the firstdopant. The concentration of indium in the melt after indium is added tothe crucible may be less than about 0.5 ppma (as measured after additionof indium and before pulling of the sample ingot) or even less thanabout 0.1 ppma, less than 0.01 ppma or less than about 0.001 ppmaindium. In some embodiments, the concentration of indium in the meltafter indium addition is from about 0.00001 ppma to about 0.5 ppma orfrom about 0.0001 ppma to about 0.1 ppma. In terms of volumeconcentration, the resulting melt may have an indium concentration ofless than about 5×10¹⁵ atoms/cm³, less than about 1×10¹⁵ atoms/cm³, lessthan about 5×10¹⁴ atoms/cm³ or less than about 1×10¹⁴ atoms/cm³. Itshould be noted that the listed amounts of first dopant are exemplaryand other amounts may be used unless stated otherwise.

In some embodiments, the first dopant is added to the polysilicon chargeas a solid-phase alloy. For example, gallium or indium may be added as asolid-phase gallium-silicon alloy or indium-silicon alloy. Suchsolid-phase gallium/indium-silicon alloys may include less than about 20wt % gallium or indium or less than about 5 wt % gallium or indium orless than about 1 wt % gallium or indium or less than 0.5 wt % galliumor indium, from about 0.001 wt % to about 5 wt % or from about 0.01 wt %to about 1 wt % gallium or indium. The amount of alloy that is added tothe crucible may depend on the size of the charge and the amount ofgallium incorporated therein. In some embodiments, about 0.5 grams toabout 50 grams or about 1 gram to about 15 grams of gallium or indiumalloy is added to the crucible.

The alloy may be prepared by weighing the desired amounts of firstdopant (e.g., gallium) and silicon and melting the materials andsolidifying in a low gradient furnace. The material may be separatedfrom its container (e.g., quartz container) and acid washed (e.g., HF).The acid washed material may be dried, crushed and sized. In someembodiments, the material is sized with a maximum size of 5 mm or less,3 mm or less or even 1 mm or less.

After polysilicon is added to the crucible, the first dopant (i.e.,gallium and/or indium) is added and the polysilicon material is melteddown. Alternatively, the first dopant may be added during or afterpolysilicon melt-down.

After the first dopant selected from gallium or indium is added and thepolysilicon charge is liquefied, a sample ingot is pulled from the meltand the resistivity of the sample ingot is measured. Generally, thesample ingot may be any suitable size and, in some embodiments, has adiameter from about 200 mm to about 300 mm and a length of at least 100mm, 300 mm, or more.

In some embodiments, the amount of first dopant added is sufficient toadjust the resistivity of the sample ingot to about 10,000 ohm-cm orless or about 5,000 ohm-cm or less or about 2,500 ohm-cm or less (e.g.,from about 500 ohm-cm to about 10,000 ohm-cm or from about 500 ohm-cm toabout 5,000 ohm-cm or from about 1000 ohm-cm to about 3000 ohm-cm).

After the sample ingot is produced, the resistivity of the sample ingotis determined. The resistivity may be measured (e.g., by a four-pointresistivity probe) at various points along the solid fraction and/oracross the diameter of a wafer or slug.

The second dopant (e.g., phosphorous or boron) is added to the crucibleafter the resistivity of the sample ingot is determined. Generally thesecond dopant that is added to the melt to achieve the targetresistivity is any n-type dopant and is typically phosphorous. In otherembodiments, depending on the measured magnitude of the resistivity ofthe sample ingot, boron dopant may be used to achieve the desired targetresistivity.

The amount of second dopant that is added is based, at least in part, onthe measured resistivity of the sample rod and a target resistivity fora prime portion 55 (FIG. 1) of the product ingot 51. The amount ofsecond dopant used may be determined based on Equations 2-5 providedabove.

In some embodiments, the target resistivity of the prime portion of theingot may be a minimum resistivity. In some embodiments, the entirelength of the ingot (e.g., length of the body of the ingot) has thetarget resistivity (e.g., minimum resistivity). In some embodiments, thetarget resistivity is a minimum resistivity of at least about 1,500 Ω-cmor, as in other embodiments, at least about 2,000 Ω-cm, at least about4,000 Ω-cm, at least about 6,000 Ω-cm, at least about 8,000 Ω-cm, atleast about 10,000 Ω-cm or from about 1,500 Ω-cm to about 50,000 ohm-cmor from about 8,000 Ω-cm to about 50,000 Ω-cm.

After the second dopant is added, the product ingot is withdrawn fromthe melt. The product ingot may have a diameter of about 150 mm or, asin other embodiments, about 200 mm, about 300 mm or more (e.g., 450 mmor more).

Compared to conventional methods, the methods of embodiments of thepresent disclosure for growing a single crystal silicon ingot haveseveral advantages. Relatively high purity polysilicon that is used toproduce relatively high resistivity single crystal silicon has a widespread in boron and phosphorous impurity amounts which causes a widespread in the intrinsic resistivity. The wide spread in resistivity andthe high-resistivity itself cause errors in the resistivity measurement.By adding gallium or indium before the sample ingot is grown, thevariation in resistivity and the resistivity itself is reduced whichreduces the error in the resistivity measurement. For example, reducedmeasurement error may be observed by adjusting the amount of gallium orindium to yield a resistivity of, for example, about 1,000 ohm-cm toabout 2,000 ohm-cm. By adding gallium before addition of the seconddopant (e.g., phosphorous), the amount of second dopant added isincreased to compensate to the desired net charge carrier concentrationwhich results in the desired resistivity. Addition of a higher amount ofsecond dopant (e.g., increase in 10 fold amount such as addition ofseveral grams rather than several milligrams of second dopant) reduceserrors in weight measurement and improves the transfer efficiencies ofsecond dopant (e.g., dopant cup to the polysilicon stack). Further,addition of first dopant such as gallium eliminates or at least delaysthe transition of the ingot type as the first dopant is characterized bya smaller segregation coefficient, even smaller than phosphorous dopant.This allows gallium to closely follow and counter the steep rise inphosphorous concentration as shown in FIG. 9. In embodiments in which asolid-phase alloy of the first dopant is used (e.g., containing lessthan 5 wt % gallium/indium), the alloy material has a larger mass andvolume relative to the pure first dopant alone which reduces error inthe measurement of the material and improves transfer efficiency. Byusing an alloy of gallium or indium, the melting temperature of thematerial is raised (e.g., from the 29.7° C. melting temperature of puregallium when gallium is used) which eases transfer into the crucible.The solid-phase alloy also stays as a solid until it is melted in thepolysilicon charge, allowing for ease of handling without the need tokeep the material (e.g., pure gallium) refrigerated or cooled to belowits melting temperature.

EXAMPLES

The processes of the present disclosure are further illustrated by thefollowing Examples. These Examples should not be viewed in a limitingsense.

Example 1: Gallium Doping to Defer Ingot Type Change

The type change in a single crystal silicon wafer resulting frombuild-up of boron and phosphorous impurity accumulation was modeled andis shown in FIG. 5. As shown in FIG. 5, type-change from P-type toN-type occurred at about 17% solidified fraction due to the accumulationof phosphorous relative to boron. Addition of gallium defers the typechange from P-type to N-type to about 62% of the solidified fraction.This indicates that gallium acts to compensate for phosphorous impurityaccumulation. Given a resistivity target of from about 10,000 ohm-cm toabout 50,000 ohm-cm, use of gallium resulted in a 40% yield improvement.

The resistivity profiles for ingots having 2.1×10¹³ atoms/cm³ boron,2.73×10¹³ atoms/cm³ phosphorous and with and without 1.0×10¹⁴ atoms/cm³gallium are shown in FIG. 6. As shown in FIG. 6, use of gallium deferredthe type change from about 70% of the solidified fraction to about 80%.

The resistivity profiles for ingots having 8×10¹² atoms/cm³ boron,1.75×10¹³ atoms/cm³ phosphorous and with and without 3×10¹⁴ atoms/cm³gallium are shown in FIG. 7. As shown in FIG. 7, when gallium was notused the type change to N-type occurred at about 10% of the solidifiedfraction. Use of gallium allowed the ingot to remain P-type throughoutthe length of the body.

The resistivity profiles for an ingot having 5.7×10¹² atoms/cm³ boron,1.52×10¹³ atoms/cm³ phosphorous and with and without 2.67×10¹⁴ atoms/cm³gallium are shown in FIG. 8. The ingot without gallium doping was N-typeand the ingot that was doped with gallium was P-type. The compositionsegregation curves for boron, phosphorus and gallium are shown in FIG.9.

The resistivity profiles for ingots having the same dopant profile asFIG. 8 were modeled with the effect of oxygen (i.e., thermal donors)being taken into account. As shown in FIG. 10, the ingot in whichthermal donors were taken into account type-changed to N-type at about75% and the ingot that did not account for thermal donors was P-typethroughout the body portion. Given the thermal donor effect, it isdesired to sustain oxygen at a relatively low value such that thermaldonor effects are managed. Increased oxygen will result in increased netresistivity, but can allow the type change to occur earlier in the bodylength. Oxygen targets below 4 nppma or even below 3.5 nppma assist insuppressing type change along with compensation dopant management.

FIG. 11 shows the resistivity profile of a gallium compensated systemconsidering the thermal donor effects. In one instance the ingotunderwent a thermal donor kill anneal to eliminate the oxygencontribution to the resistivity and in another the ingot underwent aheat treatment to fully ionize the thermal donors. As shown in FIG. 11,the measured resistivity values closely matched the modeled values.

Example 2: Gallium Alloy Formation

To facilitate the small amount of gallium used to control resistivity, amaster gallium-silicon alloy was produced. The alloy had a galliumconcentration in the range of 0.1 to 0.3 wt %. Amounts of silicon andgallium were weighed. The materials were melted and frozen in a quartzcontainer in low gradient furnace. The alloy material was separated fromthe container and acid washed in HF. The alloy was then dried, crushed,sized and cleaned to less than 3 mm. The resulting alloy material isshown in FIG. 12. The resulting gallium-silicon alloy material wassuitable for use for gallium doping as described in Example 1.

As used herein, the terms “about,” “substantially,” “essentially” and“approximately” when used in conjunction with ranges of dimensions,concentrations, temperatures or other physical or chemical properties orcharacteristics is meant to cover variations that may exist in the upperand/or lower limits of the ranges of the properties or characteristics,including, for example, variations resulting from rounding, measurementmethodology or other statistical variation.

When introducing elements of the present disclosure or the embodiment(s)thereof, the articles “a”, “an”, “the” and “said” are intended to meanthat there are one or more of the elements. The terms “comprising,”“including,” “containing” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements. The use of terms indicating a particular orientation (e.g.,“top”, “bottom”, “side”, etc.) is for convenience of description anddoes not require any particular orientation of the item described.

As various changes could be made in the above constructions and methodswithout departing from the scope of the disclosure, it is intended thatall matter contained in the above description and shown in theaccompanying drawing[s] shall be interpreted as illustrative and not ina limiting sense.

What is claimed is:
 1. A method for producing a single crystal siliconproduct ingot, the method comprising: adding polycrystalline silicon toa crucible; heating the polycrystalline silicon to cause a silicon meltto form in the crucible; adding a first dopant selected from the groupconsisting of gallium and indium to the crucible to form a silicon meltcomprising silicon and the first dopant; pulling a sample ingot from thesilicon melt comprising silicon and the first dopant, the sample ingothaving a resistivity, there being a silicon melt comprising silicon andfirst dopant disposed in the crucible after the sample ingot is pulled;measuring the resistivity of the sample ingot; adding an amount ofphosphorous as a second dopant to the silicon melt comprising siliconand the first dopant to form a silicon melt comprising silicon, thefirst dopant and phosphorous, phosphorous being added after theresistivity of the sample ingot is measured, the amount of phosphorousadded to the silicon melt being based at least in part on the measuredresistivity of the sample ingot; and pulling the single crystal siliconproduct ingot from the silicon melt comprising silicon, the first dopantand phosphorous.
 2. The method as set forth in claim 1 wherein theamount of phosphorous added to the silicon melt comprising silicon andthe first dopant is based at least in part on a target resistivity of atleast a portion of the single crystal silicon product ingot.
 3. Themethod as set forth in claim 2 wherein the target resistivity is aminimum resistivity.
 4. The method as set forth in claim 3 wherein theminimum resistivity is at least about 1,500 Ω-cm.
 5. The method as setforth in claim 2 wherein the target resistivity is a maximumresistivity.
 6. The method as set forth in claim 1 wherein the firstdopant is gallium.
 7. The method as set forth in claim 6 wherein themelt comprising gallium has a concentration of gallium in the melt aftergallium is added to the crucible, the concentration of gallium beingless than about 0.5 ppma.
 8. The method as set forth in claim 6 whereingallium is added to the crucible as a silicon-gallium alloy.
 9. Themethod as set forth in claim 1 wherein the first dopant is indium. 10.The method as set forth in claim 9 wherein the melt comprising indiumhas a concentration of indium in the melt after indium is added to thecrucible, the concentration of indium being less than about 0.5 ppma.11. The method as set forth in claim 9 wherein indium is added to thecrucible as a silicon-indium alloy.
 12. The method as set forth in claim1 wherein the measured resistivity of the sample ingot is about 10,000ohm-cm or less.
 13. The method as set forth in claim 1 wherein thepolycrystalline silicon is semiconductor grade silicon.
 14. The methodas set forth in claim 1 comprising measuring the resistivity of thesample ingot with a four-point resistivity probe.